JP4646632B2 - Method for producing composite cured silicone powder and aqueous composition - Google Patents
Method for producing composite cured silicone powder and aqueous composition Download PDFInfo
- Publication number
- JP4646632B2 JP4646632B2 JP2004560610A JP2004560610A JP4646632B2 JP 4646632 B2 JP4646632 B2 JP 4646632B2 JP 2004560610 A JP2004560610 A JP 2004560610A JP 2004560610 A JP2004560610 A JP 2004560610A JP 4646632 B2 JP4646632 B2 JP 4646632B2
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- JP
- Japan
- Prior art keywords
- cured silicone
- powder
- silicone powder
- inorganic fine
- composite cured
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000010495 camellia oil Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- 229940100463 hexyl laurate Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
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- 229940074928 isopropyl myristate Drugs 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- BORJONZPSTVSFP-UHFFFAOYSA-N tetradecyl 2-hydroxypropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)O BORJONZPSTVSFP-UHFFFAOYSA-N 0.000 description 1
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 1
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/124—Treatment for improving the free-flowing characteristics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
【技術分野】
【０００１】
本発明は、硬化シリコーン粉末および無機質微粉末を含有する複合硬化シリコーン粉末の製造方法に関し、詳しくは、優れた流動性、親水性および分散性を有する複合硬化シリコーン粉末の製造方法、および該製造方法により得られた複合硬化シリコーン粉末を含有する水性組成物に関する。
【背景技術】
【０００２】
硬化シリコーン粉末は、化粧品、塗料、インキ、熱硬化性有機樹脂、熱可塑性有機樹脂等の添加剤として使用されており、特に、熱硬化性有機樹脂の内部応力緩和剤や有機樹脂フィルムの表面潤滑剤として好適に使用されている。
【０００３】
このような硬化シリコーン粉末を製造する方法としては、例えば、シリコーンゴムをグラインダーにより粉砕する方法；液状シリコーンゴム組成物をスプレードライヤー等により噴霧した状態で硬化させる方法（特開昭５９−６８３３３号公報参照）；液状シリコーンゴム組成物を水中に分散させた状態で硬化させる方法（特開昭６２−２４３６２１号公報、特開昭６３−７７９４２号公報、特開昭６３−２０２６５８号公報、および特開昭６４−７０５５８号公報参照）が挙げられる。
しかしながら、このようにして得られた硬化シリコーン粉末は、凝集性が強いために、流動性が悪く、また、水性塗料、化粧品などの水性組成物への分散性に乏しかった。硬化シリコーン粉末が水性組成物へ均一に分散せず、凝集した状態で水性組成物中に存在すると、水性塗料の場合は、硬化シリコーン粉末による均一な艶消し効果が得られないという問題が起こり、化粧品の場合は、触感が悪くなるという問題が起こる。
【０００４】
そこで、硬化シリコーン粉末の表面に無機質微粉末を付着させて、流動性を向上させた複合硬化シリコーン粉末が提案されている（特開平４−３４８１４３号公報、特開平５−１７９１４４号公報、および特開平７−１０２０７５号公報参照）。
しかしながら、このようにして得られた複合硬化シリコーン粉末は、親水性が乏しく、これを水性組成物に配合した場合には、水性組成物に対する親和性が乏しいという問題があった。
【０００５】
また、特開平７−１９６８１５号公報には、シリコーンゴム粉末表面をポリオルガノシルセスキオキサン樹脂で被覆することが提案され、特開平９−２０８７０９号公報では、オイルを含有するシリコーン粉末を無機質微粒子で被覆することが提案されている。
しかしながら、これら複合硬化シリコーン粉末は、それぞれ、親水性や水性組成物への分散性が不十分であった。
【発明の開示】
【０００６】
本発明の目的は、優れた流動性、親水性および分散性を有する複合硬化シリコーン粉末を製造する方法を提供することにある。
【０００７】
本発明者らは、上記課題について鋭意検討した結果、本発明に到達した。すなわち、本発明の複合硬化シリコーン粉末の製造方法は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末と（Ｂ）無機質微粉末とを機械的剪断下で混合した後、これと（Ｃ）界面活性剤とを機械的剪断下で混合することを特徴とするものであり、該複合硬化シリコーン粉末は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末に（Ｂ）無機質微粉末が付着し、（Ｂ）無機質微粉末に（Ｃ）界面活性剤が付着していることを特徴とするものである。
【０００８】
また、本発明の複合硬化シリコーン粉末の製造方法において、
（Ｂ）無機質微粉末は、金属酸化物微粉末であることが望ましい。
また、（Ｂ）無機質微粉末の比表面積は、１０ｍ２／ｇ以上であることが望ましい。
また、（Ｂ）無機質微粉末は、シリカであることが望ましい。
また、（Ａ）硬化シリコーン粉末は、シリコーンゴム粉末であることが望ましい。
【０００９】
また、本発明の複合硬化シリコーン粉末の製造方法は、（Ａ）硬化シリコーン粉末と（Ｂ）無機質微粉末とを機械的剪断下で混合した後、これと（Ｃ）界面活性剤とを機械的剪断下で混合するものであり、本発明の水性組成物は、該製造方法により得られた本発明の複合硬化シリコーン粉末を用いて製造され、また、該複合硬化シリコーン粉末を含有することを特徴とするものである。
【発明を実施するための最良の形態】
【００１０】
以下、本発明について詳細に説明する。
本発明の複合硬化シリコーン粉末の製造方法は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末と（Ｂ）無機質微粉末とを機械的剪断下で混合した後、これと（Ｃ）界面活性剤とを機械的剪断下で混合することを特徴とするものであり、該複合硬化シリコーン粉末は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末に（Ｂ）無機質微粉末が付着し、（Ｂ）無機質微粉末に（Ｃ）界面活性剤が付着しているものである。
【００１１】
［（Ａ）硬化シリコーン粉末］
（Ａ）硬化シリコーン粉末とは、オルガノシランやオルガノポリシロキサンなどを架橋反応で硬化させ、粉末化したものであって、シロキサン結合を構造中に含むものである。（Ａ）硬化シリコーン粉末としては、例えば、シリコーンゲル粉末、シリコーンゴム粉末、シリコーンレジン粉末が挙げられ、特に、シリコーンゴム粉末が、硬さを様々に調整できる等、用途に合わせて種々の特性を付与できる点で、好ましい。また、（Ａ）硬化シリコーン粉末としては、例えば、付加反応、縮合反応、有機過酸化物、紫外線等により硬化して得られたものであり、特に、付加反応や縮合反応により得られた硬化シリコーン粉末であることが好ましい。
【００１２】
（Ａ）硬化シリコーン粉末の物理的特性は、特に限定されないが、これがシリコーンゴム粉末である場合には、このＪＩＳ Ａ硬度が９０未満であることが好ましく、特には、５０以下であることが好ましい。
【００１３】
（Ａ）硬化シリコーン粉末の平均粒子径は、０．１〜５００μｍの範囲内であり、好ましくは、０．１〜２００μｍの範囲内であり、特に好ましくは、０．１〜１００μｍの範囲内である。これは、平均粒子径がこの範囲より小さい硬化シリコーン粉末の表面に無機質微粉末を付着させることが困難となる傾向があり、一方、この範囲より大きい硬化シリコーン粉末を用いてなる複合硬化シリコーン粉末は、水性組成物に対する分散性が乏しくなる傾向があるためである。
【００１４】
（Ａ）硬化シリコーン粉末は、非架橋のオイルを含有していてもよい。この非架橋のオイルは、（Ａ）硬化シリコーン粉末中に単に含まれており、この粉末から自然に滲み出たり、また、有機溶剤により抽出可能なオイルのことである。非架橋のオイルとしては、例えば、非架橋のシリコーンオイル、非架橋の有機オイルが例示される。
非架橋のシリコーンオイルは、（Ａ）硬化シリコーン粉末を形成するための硬化反応に関与しなかったシリコーンオイルであり、この分子構造としては、例えば、直鎖状、一部分岐を有する直鎖状、環状、分岐鎖状が挙げられ、特に、直鎖状であることが好ましい。
非架橋のシリコーンオイルとしては、分子鎖両末端トリメチルシロキシ基封鎖ジメチルポリシロキサン、このジメチルポリシロキサンのメチル基の一部をメチル基以外のアルキル基、フェニル基、３，３，３−トリフルオロプロピル基に置換したポリシロキサン等の非反応性シリコーンオイルが一般的である。
【００１５】
また、（Ａ）硬化シリコーン粉末を形成する反応が付加反応である場合であって、（Ａ）硬化シリコーン粉末を形成するための硬化性シリコーン組成物中に、非架橋のシリコーンオイルを予め含ませておく場合には、非架橋のシリコーンオイルとしては、上記の非反応性シリコーンオイル以外に、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン、このジメチルポリシロキサンのメチル基の一部をメチル基以外のアルキル基、フェニル基、３，３，３−トリフルオロプロピル基に置換したポリシロキサン等のシリコーンオイル、さらには、この付加反応に関与し得るが、未反応として残った分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、これらのポリシロキサンのメチル基の一部をメチル基以外のアルキル基、フェニル基、３，３，３−トリフルオロプロピル基に置換したポリシロキサン等のシリコーンオイルが例示される。
【００１６】
また、（Ａ）硬化シリコーン粉末を形成する反応が縮合反応である場合であって、（Ａ）硬化シリコーン粉末を形成するための硬化性シリコーン組成物中に、非架橋のシリコーンオイルを予め含ませておく場合には、非架橋のシリコーンオイルとしては、上記の非反応性シリコーンオイル以外に、この非反応性シリコーンオイルのメチル基の一部をアルケニル基に置換したポリシロキサン等のシリコーンオイル、さらには、この縮合反応に関与し得るが、未反応として残った分子鎖両末端シラノール基封鎖ジメチルポリシロキサン、このポリシロキサンのメチル基の一部をメチル基以外のアルキル基、アルケニル基、フェニル基、３，３，３−トリフルオロプロピル基に置換したシリコーンオイルが例示される。
また、（Ａ）硬化シリコーン粉末に後から非架橋のシリコーンオイルを含浸する場合には、このシリコーンオイルの種類は特に限定されない。
【００１７】
非架橋の有機オイルとしては、流動パラフィン、ラウリン酸ヘキシル、ミリスチン酸イソプロピル、ミリスチン酸ミリスチル、ミリスチン酸セチル、ミリスチン酸２−オクチルドデシル、パルミチン酸イソプロピル、パルミチン酸２−エチルヘキシル、ステアリン酸ブチル、オレイン酸デシル、オレイン酸２−オクチルドデシル、乳酸ミリスチル、乳酸セチル、酢酸ラノリン、ステアリルアルコール、セトステアリルアルコール、オレイルアルコール、アボガド油、アルモンド油、オリブ油、カカオ油、ホホバ油、ゴマ油、サフラワー油、大豆油、ツバキ油、スクワラン、パーシック油、ヒマシ油、ミンク油、綿実油、ヤシ油、卵黄油、牛脂、豚脂、ポリプロピレングリコールモノオレート、ネオペンチルグリコール−２−エチルヘキサノエート等のグリコールエステル油；イソステアリン酸トリグリセライド、椰子油脂肪酸トリグリセライド等の多価アルコールエステル油；ポリオキシエチレンラウリルエーテル、ポリオキシプロピレンセチルエーテル等のポリオキシアルキレンエーテル油が例示される。これらの有機オイルは、（Ａ）硬化シリコーン粉末を形成するための硬化性シリコーン組成物中に予め含ませておいてもよく、（Ａ）硬化シリコーン粉末に含浸してもよい。
【００１８】
これらの非架橋のオイルは液状であり、この２５℃における粘度は、例えば、１〜１００，０００センチポイズの範囲内であることが好ましく、さらには、５〜５０，０００センチポイズの範囲内であることが好ましく、特には、５〜１０，０００センチポイズの範囲内であることが好ましい。これは、２５℃における粘度がこの範囲より小さいオイルは揮発性があり、得られる複合硬化シリコーン粉末に継続的な撥水性を付与しにくくなる傾向があり、一方、この範囲より大きいオイルによると、平均粒子径が１００μｍ以下である硬化シリコーン粉末を形成しにくくなる傾向があったり、硬化シリコーン粉末に含浸しにくくなる傾向があるためである。このような非架橋のオイルとしては、硬化シリコーン粉末との親和性が優れ、継続的な撥水性を複合硬化シリコーン粉末に付与することができることから、上記のシリコーンオイルであることが好ましい。
【００１９】
（Ａ）硬化シリコーン粉末に含有されている非架橋のオイルの含有量は、例えば、非架橋のオイルを含む（Ａ）硬化シリコーン粉末中、８０質量％以下であり、１０〜５０質量％の範囲内であることが好ましい。これは、（Ａ）硬化シリコーン粉末中の非架橋のオイルの含有量がこの範囲より多くなると、（Ａ）硬化シリコーン粉末の機械的強度が低下したり、得られる複合硬化シリコーン粉末から非架橋のオイルが常態においても滲み出てしまう傾向があるためである。一方、（Ａ）硬化シリコーン粉末中の非架橋のオイルの含有量が１０質量％より少なくなると、得られる複合硬化シリコーン粉末に十分な親水性を付与しにくくなる傾向がある。
【００２０】
（Ａ）硬化シリコーン粉末を調製する方法としては、例えば、下記（ｉ）〜（ｉｉｉ）等の硬化性シリコーン組成物を硬化させて得られたシリコーン硬化物をグラインダー等の粉砕機により粉砕する方法；下記（ｉ）〜（ｉｉｉ）等の硬化性シリコーン組成物をスプレードライヤー等の噴霧機により噴霧して硬化させる方法；下記（ｉ）〜（ｉｉｉ）等の硬化性シリコーン組成物を水または界面活性剤水溶液中に分散させて硬化させる方法が挙げられる。
【００２１】
（ｉ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン、非架橋性のオイル、および白金系化合物からなる付加反応硬化性シリコーン組成物。
（ｉｉ）一分子中に少なくとも２個のケイ素原子に結合する水酸基またはアルコキシ基、オキシム基、アセトキシ基、アミノキシ基等の加水分解性基を有するオルガノポリシロキサン、一分子中に少なくとも３個のケイ素原子に結合するアルコキシ基、オキシム基、アセトキシ基、アミノキシ基等の加水分解性基を有するシラン系架橋剤、非架橋性のオイル、および有機錫化合物、有機チタン化合物等の縮合反応触媒からなる縮合反応硬化性シリコーン組成物。
（ｉｉｉ）一分子中に少なくとも１個のアルケニル基を有するジオルガノポリシロキサン、非架橋性のオイル、および有機過酸化物からなる有機過酸化物硬化性シリコーン組成物。
【００２２】
これら（Ａ）硬化シリコーン粉末を調製する方法の中でも、水性組成物に対する分散性に優れた球状の（Ａ）硬化シリコーン粉末を得ることができることから、硬化性シリコーン組成物を水または界面活性剤水溶液中に分散させて硬化させる方法が特に好ましい。
【００２３】
硬化性シリコーン組成物の水系分散液を調製するためには、例えば、ホモジナイザー、コロイドミル等の撹拌装置や超音波振動機等の混合装置を用いることができる。この際、硬化性シリコーン組成物の水系分散液を調製する前に、硬化性シリコーン組成物を予め冷却して、その硬化性を制御することが好ましい。
【００２４】
また、水系分散液中で硬化性シリコーン組成物を粒子状として安定させるためには界面活性剤の水溶液を用いることが好ましい。界面活性剤の添加量は、硬化性シリコーン組成物１００質量部に対して０．１〜２０質量部であることが好ましく、０．５〜１０質量部であることがより好ましく、０．５〜５質量部が特に好ましい。ここで添加される界面活性剤は、後述する［（Ｃ）界面活性剤］とは異なるものであり、かつ任意成分である。また、水の添加量は、硬化性シリコーン組成物１００質量部に対して４０〜２０００質量部であることが好ましく、特に、４０〜１０００質量部であることが好ましい。これは、水の添加量が硬化性シリコーン組成物１００質量部に対して４０質量部未満であると均一な硬化性シリコーン組成物の水系分散液を形成することが困難であり、また、これが２０００質量部を超えると、（Ａ）硬化シリコーン粉末の生産性が著しく悪化するためである。
【００２５】
また、使用する水は、硬化性シリコーン組成物の水系分散液が安定しやすいことから、金属イオンやハロゲンイオンが少なく、電気伝導度が１μＳ／ｃｍ以下であることが好ましく、特に、電気伝導度が０．５μＳ／ｃｍ以下であるイオン交換水であることが好ましい。
【００２６】
次いで、上記の方法により調製された硬化性シリコーン組成物の水系分散液を、加熱または室温で放置することにより、この水分散液中の硬化性シリコーン組成物を硬化させて、（Ａ）硬化シリコーン粉末の水系分散液を調製することができる。
硬化性シリコーン組成物の水系分散液を加熱する場合には、その加熱温度は１００℃以下であることが好ましく、特に、１０〜９５℃であることが好ましい。また、硬化性シリコーン組成物の水系分散液を加熱する方法としては、例えば、この水系分散液を直接加熱する方法、この水系分散液を熱水中へ添加する方法が挙げられる。
【００２７】
次いで、（Ａ）硬化シリコーン粉末の水系分散液から水を除去することにより、（Ａ）硬化シリコーン粉末を調製することができる。（Ａ）硬化シリコーン粉末の水系分散液から水を除去する方法としては、例えば、真空乾燥機、熱風循環式オーブン、スプレードライヤーを用いて乾燥する方法が挙げられる。
【００２８】
［（Ｂ）無機質微粉末］
（Ｂ）無機質微粉末は、少なくともその一部が（Ａ）硬化シリコーン粉末の表面に付着した状態で、本発明の複合硬化シリコーン粉末中に存在するものである。ここでいう付着とは、（Ａ）硬化シリコーン粉末の全体を覆うように、（Ａ）硬化シリコーン粉末の表面に（Ｂ）無機質微粉末が被覆されている状態、または（Ａ）硬化シリコーン粉末の表面の一部に（Ｂ）無機質微粉末が偏在している状態を指す。また、一部の（Ｂ）無機質微粉末は、（Ａ）硬化シリコーン粉末の表面から脱落した状態で本発明の複合硬化シリコーン粉末中に存在していても構わない。
【００２９】
（Ｂ）無機質微粉末は、少なくともその一部が（Ａ）硬化シリコーン粉末の表面に付着していることにより、（Ａ）硬化シリコーン粉末の凝集を抑え、本発明の複合硬化シリコーン粉末の流動性、分散性を向上させるものである。
（Ｂ）無機質微粉末としては、例えば、酸化ケイ素、酸化チタン、酸化アルミニウム、酸化ジルコニウム、酸化アンチモン等の金属酸化物微粉末；窒化ホウ素、窒化アルミニウム等の金属窒化物微粉末；水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物微粉末；炭酸カルシウムなどの金属炭酸塩；ニッケル、コバルト、鉄、銅、金、銀などの金属微粒子；マイカ、タルク、カオリナイト、スメクタイト、ハロイサイト、パイロフィライト、バーミキュライト、モンモリロナイトなどの粘土鉱物；その他、硫化物微粉末、塩化物微粉末が挙げられる。中でも、入手の容易さからコスト的に有利であるので、金属酸化物微粉末が好ましく、特に、シリカ微粉末が好ましい。また、（Ｂ）無機質微粉末の表面は、オルガノアルコキシシラン、オルガノクロロシラン、オルガノシラザン等の有機ケイ素化合物により予め疎水化処理されていてもよい。
【００３０】
（Ｂ）無機質微粉末の粒子径は、（Ａ）硬化シリコーン粉末の表面に付着できる粒子径であればよく、具体的には、（Ａ）硬化シリコーン粉末の平均粒子径に対して１／１０以下の粒子径であることが好ましい。また、（Ｂ）無機質微粉末は、二次凝集粒子でもよいが、その分散性付与効果の点から、この比表面積が１０ｍ２／ｇ以上であることが好ましい。ここで、比表面積は、ＢＥＴ比表面積による値である。
【００３１】
［（Ｃ）界面活性剤］
（Ｃ）界面活性剤は、少なくともその一部が（Ｂ）無機質微粉末の表面に付着した状態で、本発明の複合硬化シリコーン粉末中に存在するものである。ここでいう付着とは、（Ｂ）無機質微粉末の表面を覆うように、（Ｂ）無機質微粉末の表面に（Ｃ）界面活性剤が被覆または吸着されている状態、または（Ｂ）無機質微粉末の表面の一部に（Ｃ）界面活性剤が偏在している状態を指す。また、一部の（Ｃ）界面活性剤は、（Ａ）硬化シリコーン粉末の表面に付着、吸収された状態で本発明の複合硬化シリコーン粉末中に存在していても構わない。
【００３２】
（Ｃ）界面活性剤は、（Ｂ）無機質微粉末の表面に付着した状態で、本発明の複合硬化シリコーン粉末中に存在することにより、本発明の複合硬化シリコーン粉末の親水性を向上させる成分である。
（Ｃ）界面活性剤としては、例えば、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤およびこれらの二種以上の混合物が挙げられる。中でも、得られた複合硬化シリコーン粒子の分散性の点で、ノニオン系界面活性剤であることが好ましい。ノニオン系界面活性剤としては、親油性あるいは親水性のノニオン系界面活性剤を用いることができる。
【００３３】
親油性ノニオン界面活性剤としては、例えば、ソルビタンモノオレエート、ソルビタンモノイソステアレート、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンセスキオレエート、ソルビタントリオレエート、ペンタ−２−エチルヘキシル酸ジグリセロールソルビタン、テトラ−２−エチルヘキシル酸ジグリセロールソルビタン等のソルビタン脂肪酸エステル類；モノ綿実油脂肪酸グリセリン、モノエルカ酸グリセリン、セスキオレイン酸グリセリン、モノステアリン酸グリセリン、α，α´−オレイン酸ピログルタミン酸グリセリン、モノステアリン酸グリセリン、リンゴ酸グリセリン等のグリセリン脂肪酸類；モノステアリン酸プロピレングリコール等のプロピレングリコール脂肪酸エステル類、硬化ヒマシ油誘導体、グリセリンアルキルエーテル等が挙げられる。
【００３４】
親水性ノニオン界面活性剤としては、例えば、ポリオキシエチレン（以下、ＰＯＥ）ソルビタンモノオレエート、ＰＯＥソルビタンモノステアレート、ＰＯＥソルビタンモノオレート、ＰＯＥソルビタンテトラオレエート等のＰＯＥソルビタン脂肪酸エステル類；ＰＯＥソルビットモノラウレート、ＰＯＥソルビットモノオレエート、ＰＯＥソルビットペンタオレエート、ＰＯＥソルビットモノステアレート等のＰＯＥソルビット脂肪酸エステル類；ＰＯＥグリセリンモノステアレート、ＰＯＥグリセリンモノイソステアレート、ＰＯＥグリセリントリイソステアレート等のＰＯＥグリセリン脂肪酸エステル類；ＰＯＥモノオレエート、ＰＯＥモノステアレート、ＰＯＥジステアレート、ＰＯＥモノジオレエート、システアリン酸エチレングリコール等のＰＯＥ脂肪酸エステル類；ＰＯＥラウリルエーテル、ＰＯＥオレイルエーテル、ＰＯＥステアリルエーテル、ＰＯＥベヘニルエーテル、ＰＯＥ−２−オクチルドデシルエーテル、ＰＯＥコレスタノールエーテル等のＰＯＥアルキルエーテル類；ＰＯＥオクチルフェニルエーテル、ＰＯＥノニルフェニルエーテル、ＰＯＥジノニルフェニルエーテル等のＰＯＥアルキルフェニルエーテル類；プルロニック（ポリオキシエチレン・ポリオキシプロピレングリコール）等のプルロニック型類、ＰＯＥ・ポリオキシプロピレン（以下、ＰＯＰ）セチルエーテル、ＰＯＥ・ＰＯＰ−２−デシルテトラデシルエーテル、ＰＯＥ・ＰＯＰモノブチルエーテル、ＰＯＥ・ＰＯＰ水添ラノリン、ＰＯＥ・ＰＯＰグリセリンエーテル等のＰＯＥ・ＰＯＰアルキルエーテル類；テトロニック等のテトラＰＯＥ・テトラＰＯＰエチレンジアミン縮合物類；ＰＯＥヒマシ油、ＰＯＥ硬化ヒマシ油、ＰＯＥ硬化ヒマシ油モノイソステアレート、ＰＯＥ硬化ヒマシ油トリイソステアレート、ＰＯＥ硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、ＰＯＥ硬化ヒマシ油マレイン酸等のＰＯＥヒマシ油硬化ヒマシ油誘導体；ＰＯＥソルビットミツロウ等のＰＯＥミツロウ・ラノリン誘導体；ヤシ油脂肪酸ジエタノールアミド、ラウリン酸モノエタノールアミド、脂肪酸イソプロパノールアミド等のアルカノールアミド、ＰＯＥプロピレングリコール脂肪酸エステル、ＰＯＥアルキルアミン、ＰＯＥ脂肪酸アミド、ショ糖脂肪酸エステル、ＰＯＥノニルフェニルホルムアルデヒド縮合物、アルキルエトキシジメチルアミンオキシド、トリオレイルリン酸等が挙げられる。
【００３５】
シリコーン系界面活性剤としては、ジメチルポリシロキサン−ポリエチレングリコール類、ジメチルポリシロキサンポリエチレン類、ジメチルポリシロキサンポリエチレングリコール共重合体類、ジメチルポリシロキサン・メチル（ポリオキシエチレン）シロキサン共重合体類等が挙げられる。
これらノニオン系界面活性剤の中でも、配合時に液体として取り扱いやすい点から、ポリエチレンオキサイド基含有のノニオン系界面活性剤が好ましく、特に、ポリエチレンオキサイドのアルキルエーテルとして、このアルキルエーテル中のアルキル基の少なくとも１０質量％が炭素数１３のアルキル基であるもの、あるいは、ポリオキシエチレンソルボタンモノラウリルエーテルが好ましい。これらノニオン性活性剤の中から一種または二種以上を任意に選択されて用いることができる。
【００３６】
［複合硬化シリコーン粉末］
（Ａ）硬化シリコーン粉末に対する、（Ｂ）無機微粒子や（Ｃ）界面活性剤の付着量は、調整した複合硬化シリコーン粒子が十分な流動性および親水性を有する程度であればよく、特に限定されない。また、（Ａ）硬化シリコーン粉末の粒径により、（Ｂ）無機微粒子や（Ｃ）界面活性剤の付着量は変動するが、（Ｂ）無機微粒子および（Ｃ）界面活性剤の付着量は、好ましくは、（Ａ）硬化シリコーン粉末１００質量部に対して、（Ｂ）無機微粒子が０．１〜３０質量部、（Ｃ）界面活性剤が０．１〜３０質量部である。特に好ましくは、（Ａ）硬化シリコーン粉末１００質量部に対して、（Ｂ）無機微粒子０．２〜１０質量部、（Ｃ）界面活性剤が０．２〜１０質量部である。これは、（Ｂ）無機微粒子や（Ｃ）界面活性剤の量がこの範囲外では、流動性が悪化したり、親水性が向上しにくいという傾向があるためである。
【００３７】
次に、本発明の複合硬化シリコーン粉末の製造方法を詳細に説明する。
本発明の複合硬化シリコーン粉末は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末と（Ｂ）無機質微粉末とを機械的剪断下で混合した後、これと（Ｃ）界面活性剤とを機械的剪断下で混合することにより製造される。
機械的剪断下で、これら（Ａ）〜（Ｃ）成分を混合する装置としては、例えば、ヘンシェルンミキサー、スーパーミキサーが挙げられる。
また、これら（Ａ）〜（Ｃ）成分を混合する際の温度は、特に限定されず、例えば、室温下で行うこともできる。また、混合時間は、流動性の乏しい（Ａ）硬化シリコーン粉末が、この表面に（Ｂ）無機質微粉末が付着することにより流動性を示すようになるので、この状態の変化を観察することにより適宜決定することが必要である。
【００３８】
本発明の複合硬化シリコーン粉末の製造方法においては、（Ａ）硬化シリコーン粉末と（Ｂ）無機微粉末とをあらかじめ混合し、その後、これに（Ｃ）界面活性剤を加えて、これらを混合する。これは、（Ａ）硬化シリコーン粉末の表面に付着した（Ｂ）無機微粒子に、（Ｃ）界面活性剤が局在化して、複合硬化シリコーン粉末の親水性を向上さるためである。
【００３９】
本発明の複合硬化シリコーン粉末の製造方法における、（Ｂ）無機質微粉末の添加量は、（Ａ）硬化シリコーン粉末の表面を被覆するに十分な量であればよく、また、（Ａ）硬化シリコーン粉末に含有されている非架橋のオイルの含有量によっても異なるが、通常、（Ａ）硬化シリコーン粉末１００質量部に対して０．１〜１００質量部であることが好ましく、特に、１〜５０質量部であることが好ましい。
【００４０】
本発明の複合硬化シリコーン粉末の製造方法における、（Ｃ）界面活性剤の添加量は、複合硬化シリコーン粉末に十分な親水性を付与する量であればよく、また、（Ａ）硬化シリコーン粉末に添加される（Ｂ）無機質微粉末の配合量によっても異なるが、通常、（Ａ）硬化シリコーン粉末１００質量部に対して０．１〜１００質量部であることが好ましく、特に、０．５〜５０質量部であることが好ましい。
【００４１】
［水性組成物］
本発明の水性組成物は、本発明の複合硬化シリコーン粉末を含有する水性組成物である。
本発明の複合硬化シリコーン粉末を配合する水性組成物としては、水性媒体に分散した硬化性樹脂組成物、非硬化性樹脂組成物や、水性分散体とした化粧品などの液状組成物を例示できる。水性組成物中の水の量は、特に限定はされず、本発明の複合硬化シリコーン粉末が水相に分散しやすいことから、マトリックス相として水性媒体が存在する量でよい。
【００４２】
以上説明した本発明の複合硬化シリコーン粉末は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末に（Ｂ）無機質微粉末が付着し、（Ｂ）無機質微粉末に（Ｃ）界面活性剤が付着しているものであるので、（Ｂ）無機質微粉末による流動性、分散性の向上が損なわれることなく、（Ｃ）界面活性剤によって親水性が向上している。すなわち、（Ａ）硬化シリコーン粉末の表面に（Ｂ）無機質微粉末が存在しない状態で、（Ｃ）界面活性剤のみを（Ａ）硬化シリコーン粉末の表面に付着させると、（Ｃ）界面活性剤によって（Ａ）硬化シリコーン粉末の凝集を助長して分散性を悪くするが、（Ｂ）無機質微粉末を（Ａ）硬化シリコーン粉末の表面に付着させることにより、（Ｃ）界面活性剤が（Ｂ）無機質微粉末に偏在して、（Ｃ）界面活性剤による（Ａ）硬化シリコーン粉末の凝集が抑えられると同時に、（Ｃ）界面活性剤による親水性が複合硬化シリコーン粉末に付与される。
【００４３】
本発明の複合硬化シリコーン粉末は、優れた流動性、親水性および分散性を有するため、水性組成物に対する親和性や分散性に優れている。したがって、本発明の複合硬化シリコーン粉末は、水性塗料や水性化粧品などの水性組成物の艶消し、感触向上、クラック防止、低弾性化などを目的とした添加剤や改質剤として利用することができる。
【００４４】
［実施例］
本発明の複合硬化シリコーン粉末およびその製造方法を実施例により詳細に説明する。
本実施例中の粘度は、２５℃において測定した値である。
（Ａ）硬化シリコーン粉末および複合硬化シリコーン粉末の特性は次のようにして測定した。
［硬化シリコーン粉末のＪＩＳ Ａ硬さ］
（Ａ）硬化シリコーン粉末の原料である硬化性シリコーン組成物をシート状に硬化させて、この硬さをＪＩＳ Ｋ ６３０１に規定されるＪＩＳ Ａ硬度計により測定した。
【００４５】
［硬化シリコーン粉末中の非架橋のオイルの含有量］
（Ａ）硬化シリコーン粉末１００ｇにトルエン１０００ｇを加えて分散液を調製し、この分散液を攪拌機、例えば、ホモディスパーを用いて１０００ｒｐｍで１０分間、さらに５００ｒｐｍで１０分間攪拌した後、これを室温で１２時間静置した。その後、この分散液を再びホモディスパーを用いて５００ｒｐｍで１０分間攪拌した。この分散液を濾紙により濾過して濾液を採取した。そして、濾紙上に残った硬化シリコーン粉末にトルエン７５０ｇを加えて分散液を調製し、この分散液をホモディスパーを用いて１０００ｒｐｍで１０分間攪拌した。この分散液を濾紙により濾過して濾液を採取した。この濾液を先に採取した濾液と合わせて、エバポレータを用いて８０℃で７０ｍｍＨｇの条件下でトルエンを留去した。得られたオイルの粘度、および質量を測定した。また、このオイルをプロトン核磁気共鳴スペクトル分析、ゲルパーミエーションクロマトグラフ分析、および赤外分光分析して、このオイルの成分を特定した。
【００４６】
［平均粒子径］
（Ａ）硬化シリコーン粉末または複合硬化シリコーン粉末の水分散液あるいはエタノール分散液を、レーザー回折式粒度分布測定器（堀場製作所のＬＡ−５００）により測定し、メジアン径（累積分布の５０％に相当する粒径、５０％粒径）を平均粒径とした。
［流動性］
（Ａ）硬化シリコーン粉末または複合硬化シリコーン粉末を、アルパイン社製エアジェットシーブふるい機を使用して、１００メッシュ（目開き＝１５０μｍ）にてメッシュオンした、これらの粉末の質量％を測定することにより評価した。
【００４７】
［親水性］
１００ｍｌの水に（Ａ）硬化シリコーン粉末または複合硬化シリコーン粉末１ｇを加えて、これを撹拌機で混合した。（Ａ）硬化シリコーン粉末または複合硬化シリコーン粉末が水になじまず、水面に浮いたままでいるものを撥水性として（××）で示し、また、水になじむが水中に分散しないものを（×）、水中に分散していくものを（○）とした。
【００４８】
本実施例で用いた各成分は以下の通りである。
［（Ａ）硬化シリコーン粉末］
（Ａ−１）付加硬化型ポリジメチルシロキサンのシリコーンゴム粉末：ノニオン系界面活性剤０．２質量％含有、２０〜３０量体のポリジメチルシロキサン環状体を２．８質量％含有、平均粒径４μｍ、ＪＩＳ−Ａ硬度：３０。
（Ａ−２）付加硬化型ポリジメチルシロキサンのシリコーンゴム粉末：ノニオン系界面活性剤１．５質量％含有、２０〜３０量体のポリジメチルシロキサン環状体を２．８質量％含有、平均粒径４μｍ、ＪＩＳ−Ａ硬度：３０。
【００４９】
［（Ｂ）無機微粒子］
アエロジル２００：日本アエロジル社製、平均１次粒径５〜１５ｎｍ、ＢＥＴ比表面積２００ｍ２／ｇ、乾式法シリカ、表面シラノール密度４．２個／ｎｍ２。
［（Ｃ）界面活性剤］
エチレンオキサイド（１２モル付加）の２級ドデシルエーテルと２級トリデシルエーテルの混合物：ドデシル基４３質量％、トリデシル基５７質量％、ＨＬＢ＝１４．５
【００５０】
［実施例１］
スーパーミキサー（ヘンシェル型ミキサー、カワタ社製Ｖ−２０、内容積２０Ｌ）に（Ａ−１）シリコーンゴム粉末を投入し、室温で回転数２０００回転で約２分間攪拌して、ブロック状の塊を粉砕した。これに、（Ｂ）無機微粒子を投入して室温で回転数２０００回転で３分間混合し、さらに（Ｃ）界面活性剤を投入して、室温で回転数２０００回転で２分間混合した。ここで、（Ａ−１）シリコーンゴム粉末、（Ｂ）無機微粒子および（Ｃ）界面活性剤は、合計量が１ｋｇとなるように、質量比（Ａ−１／Ｂ／Ｃ）＝２０／２．９／１．１で配合した。
得られた複合硬化シリコーン粉末の親水性および流動性を評価し、表１に記載した。
【００５１】
［実施例２、比較例１〜４］
（Ａ）硬化シリコーン粉末の種類および配合量、（Ｂ）無機微粒子および（Ｃ）界面活性剤の配合量を表１に示すように変更した以外は、実施例１と同様にして複合硬化シリコーン粉末または硬化シリコーン粉末を得た。
得られた複合硬化シリコーン粉末および硬化シリコーン粉末の親水性および流動性を評価し、表１に記載した。
【００５２】
【表１】
［実施例３］
実施例１の複合硬化シリコーン粒子４０質量部、シリコーン処理酸化チタン１質量部、ｐ−メトキシ桂皮酸オクチル５質量部、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルポリシロキサン１０質量部、ポリオキシエチレン（４０モル付加物）硬化ヒマシ油３質量部、スクワラン３０質量部、グリセリン５質量部、ミツロウ３質量部、防腐剤適量、香料適量および精製水適量を、ミル（小型粉砕機ＳＭ−１、井内盛栄堂社製、内容積５８．５ｃｃ）で５分間撹拌して、実施例３のクリーム状化粧品を調製した。この化粧品の評価結果を表２に示した。
ここで、化粧品中の複合硬化シリコーン粒子の粒径は、ガラス板に広げた化粧品中の粒子を光学顕微鏡で観察した個数で計算した。配合性はクリーム状化粧品の粘度上昇の度合いで判断した。すなわち、分散不良は大きな粘度上昇を認めたものである。
【００５４】
［実施例４、比較例５〜７］
複合硬化シリコーン粒子を、実施例２、比較例１、比較例２、比較例４の複合硬化シリコーン粒子に変えた以外は、実施例３と同様にして、実施例４、比較例５〜７の化粧品を調製した。この化粧品の評価結果を表２に示した。
【００５５】
【表２】
［実施例５］
実施例１の複合硬化シリコーン粒子２０質量部と水性塗料（カンペパピオ社製水性つやあり１回塗り、空色、アクリル樹脂系塗料）１００質量部をデンタルミキサーで２０秒間混合攪拌して、実施例５の水性塗料組成物を調製した。この水性塗料組成物をアルミ板に、アルミ板に貼られたセロハンテープ（４０μｍ厚み）で塗膜の厚みを制御しながら、塗りつけた後、室温でドラフトに１週間放置して乾燥した。乾燥塗膜の厚みは約２０〜５０μｍであった。この水性塗料組成物の評価結果を実施例３と同様にして、表３に示した。
ここで、塗膜中の硬化シリコーン粒子の分散状態は、塗膜中の粒子を光学顕微鏡で観察した個数で計算した。配合性は、塗料組成物の粘度上昇の度合いで判断した。すなわち、分散不良は大きな粘度上昇を認めたものである。
【００５７】
［実施例６、比較例８、９］
複合硬化シリコーン粒子を実施例２、比較例２あるいは比較例３の複合硬化シリコーン粒子に変えた以外は、実施例５と同様にして、実施例６、比較例８、比較例９の水性塗料組成物を調製した。この水性塗料組成物の評価結果を表３に示した。
【００５８】
【表３】
以上説明したように、本発明の製造方法により得られた複合硬化シリコーン粉末は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末に（Ｂ）無機質微粉末が付着し、（Ｂ）無機質微粉末に（Ｃ）界面活性剤が付着しているものであるので、優れた流動性、親水性および分散性を有する。このような複合硬化シリコーン粉末を添加した水性塗料は、均一な艶消し効果があり、また、このような複合硬化シリコーン粉末を添加した水性化粧品は、感触が良好であるという利点を有する。
【００６０】
また、本発明の複合硬化シリコーン粉末の製造方法は、（Ａ）平均粒子径が０．１〜５００μｍである硬化シリコーン粉末と（Ｂ）無機質微粉末とを機械的剪断下で混合した後、これと（Ｃ）界面活性剤とを機械的剪断下で混合するものであるので、優れた流動性、親水性および分散性を有する。
また、（Ｂ）無機質微粉末が、金属酸化物微粉末、特にシリカであれば、その入手の容易さからコスト的に有利である。
また、（Ｂ）無機質微粉末の比表面積が、１０ｍ２／ｇ以上であれば、さらに優れた流動性を付与することができるので好適である。
また、（Ａ）硬化シリコーン粉末が、シリコーンゴム粉末であれば、用途に合わせた様々な特性を付与することができるので好適である。
【００６１】
また、本発明の複合硬化シリコーン粉末の製造方法において、（Ａ）硬化シリコーン粉末と（Ｂ）無機質微粉末とを機械的剪断下で混合した後、これと（Ｃ）界面活性剤とを機械的剪断下で混合するようにすれば、流動性、親水性および分散性がさらに向上した複合硬化シリコーン粉末を得ることができる。
また、本発明の水性組成物は、本発明の製造方法により得られた複合硬化シリコーン粉末を含有するものであるので、均一な艶消し効果を有する水性塗料、感触が良好な水性化粧品を得ることができる。【Technical field】
[0001]
The present invention relates to a composite cured silicone powder containing a cured silicone powder and an inorganic fine powder.EndMore specifically, the composite cured silicone powder having excellent fluidity, hydrophilicity and dispersibility.EndManufacturing method, andObtained by the production methodThe present invention relates to an aqueous composition containing a composite cured silicone powder.
[Background]
[0002]
Cured silicone powder is used as an additive for cosmetics, paints, inks, thermosetting organic resins, thermoplastic organic resins, etc., especially for internal stress relaxation of thermosetting organic resins and surface lubrication of organic resin films. It is preferably used as an agent.
[0003]
As a method for producing such a cured silicone powder, for example, a method in which silicone rubber is pulverized with a grinder; a method in which a liquid silicone rubber composition is cured while sprayed with a spray dryer or the like (Japanese Patent Laid-Open No. 59-68333) A method of curing a liquid silicone rubber composition dispersed in water (Japanese Patent Laid-Open No. 62-243621, Japanese Patent Laid-Open No. 63-77942, Japanese Patent Laid-Open No. 63-202658, and Japanese Patent Laid-Open No. 63-202658) No. 64-70558).
However, the cured silicone powder obtained in this way has strong cohesiveness, so it has poor fluidity and is poor in dispersibility in aqueous compositions such as aqueous paints and cosmetics. If the cured silicone powder is not uniformly dispersed in the aqueous composition but is present in an aggregated state in the aqueous composition, in the case of an aqueous paint, there is a problem that a uniform matte effect by the cured silicone powder cannot be obtained, In the case of cosmetics, there is a problem that the tactile sensation becomes worse.
[0004]
Therefore, composite cured silicone powders having improved fluidity by attaching an inorganic fine powder to the surface of the cured silicone powder have been proposed (Japanese Patent Laid-Open Nos. 4-348143, 5-179144, and the like). (See Kaihei 7-102075).
However, the composite cured silicone powder obtained in this way has a poor hydrophilicity, and when it is blended with an aqueous composition, there is a problem that the affinity for the aqueous composition is poor.
[0005]
Japanese Patent Application Laid-Open No. 7-196815 proposes coating the surface of a silicone rubber powder with a polyorganosilsesquioxane resin, and Japanese Patent Application Laid-Open No. 9-208709 discloses an inorganic fine particle containing an oil-containing silicone powder. It has been proposed to coat with.
However, these composite cured silicone powders have insufficient hydrophilicity and dispersibility in aqueous compositions, respectively.
DISCLOSURE OF THE INVENTION
[0006]
An object of the present invention is to provide a composite cured silicone powder having excellent fluidity, hydrophilicity and dispersibilityEndIt is to provide a method of manufacturing.
[0007]
As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is,The method for producing a composite cured silicone powder of the present invention comprises: (A) a cured silicone powder having an average particle size of 0.1 to 500 μm and (B) an inorganic fine powder are mixed under mechanical shearing; C) A surfactant is mixed under mechanical shearing, and the composite cured silicone powder comprises:(A) (B) inorganic fine powder adheres to the cured silicone powder having an average particle size of 0.1 to 500 μm, and (C) a surfactant adheres to (B) inorganic fine powder. To do.
[0008]
The composite cured silicone powder of the present inventionIn the manufacturing method of
(B) The inorganic fine powder is desirably a metal oxide fine powder.
The specific surface area of the inorganic fine powder (B) is desirably 10 m2 / g or more.
Further, (B) the inorganic fine powder is desirably silica.
The (A) cured silicone powder is preferably a silicone rubber powder.
[0009]
The method for producing the composite cured silicone powder of the present invention is as follows.,A mixture of (A) cured silicone powder and (B) fine inorganic powder under mechanical shearing and then mixing this with (C) a surfactant under mechanical shearing.AndThe aqueous composition of the present invention comprisesThe composite cured silicone powder of the present invention obtained by the manufacturing method is used, and the composite cured silicone powder is contained.
BEST MODE FOR CARRYING OUT THE INVENTION
[0010]
Hereinafter, the present invention will be described in detail.
The method for producing a composite cured silicone powder of the present invention comprises: (A) a cured silicone powder having an average particle size of 0.1 to 500 μm and (B) an inorganic fine powder are mixed under mechanical shearing; C) a surfactant and mixed under mechanical shearing,In the composite cured silicone powder, (B) inorganic fine powder adheres to (A) cured silicone powder having an average particle size of 0.1 to 500 μm, and (C) surfactant adheres to (B) inorganic fine powder. It is what.
[0011]
[(A) Cured silicone powder]
(A) Cured silicone powder is a powder obtained by curing organosilane, organopolysiloxane, or the like by a crosslinking reaction, and includes a siloxane bond in the structure. (A) Examples of the cured silicone powder include silicone gel powder, silicone rubber powder, and silicone resin powder. In particular, the silicone rubber powder has various properties depending on the application, such as various hardness adjustments. It is preferable at the point which can provide. The cured silicone powder (A) is obtained by curing with, for example, an addition reaction, a condensation reaction, an organic peroxide, an ultraviolet ray, etc., and in particular, a cured silicone obtained by an addition reaction or a condensation reaction. A powder is preferred.
[0012]
(A) The physical properties of the cured silicone powder are not particularly limited, but when this is a silicone rubber powder, the JIS A hardness is preferably less than 90, and particularly preferably 50 or less. .
[0013]
(A) The average particle diameter of the cured silicone powder is in the range of 0.1 to 500 μm, preferably in the range of 0.1 to 200 μm, and particularly preferably in the range of 0.1 to 100 μm. is there. This tends to make it difficult to attach the inorganic fine powder to the surface of the cured silicone powder having an average particle size smaller than this range, while the composite cured silicone powder using a cured silicone powder larger than this range This is because the dispersibility with respect to the aqueous composition tends to be poor.
[0014]
(A) The cured silicone powder may contain non-crosslinked oil. This non-crosslinked oil is an oil that is simply contained in the (A) cured silicone powder, and oozes naturally from the powder, or can be extracted with an organic solvent. Examples of non-crosslinked oils include non-crosslinked silicone oils and non-crosslinked organic oils.
Non-crosslinked silicone oil is (A) a silicone oil that did not participate in the curing reaction to form a cured silicone powder. The molecular structure of the non-crosslinked silicone oil is, for example, linear, partially branched linear, Examples thereof include cyclic and branched chains, and a straight chain is particularly preferable.
Non-crosslinked silicone oils include trimethylsiloxy group-blocked dimethylpolysiloxanes at both molecular chain ends, a part of the methyl groups of this dimethylpolysiloxane being alkyl groups other than methyl groups, phenyl groups, 3,3,3-trifluoropropyl Non-reactive silicone oils such as polysiloxanes substituted on groups are common.
[0015]
In addition, (A) the reaction for forming the cured silicone powder is an addition reaction, and (A) the curable silicone composition for forming the cured silicone powder contains an uncrosslinked silicone oil in advance. In addition to the above non-reactive silicone oil, the non-crosslinked silicone oil may be a silanol-blocked dimethylpolysiloxane having both molecular chains blocked, and a part of the methyl group of this dimethylpolysiloxane other than the methyl group. Silicone oil such as polysiloxane substituted with an alkyl group, phenyl group, 3,3,3-trifluoropropyl group, and dimethylvinylsiloxy at both ends of the molecular chain that may be involved in this addition reaction but remained unreacted. Capped dimethylpolysiloxane, molecular chain both ends trimethylsiloxy group capped dimethylsiloxane methylvini Siloxane copolymer, dimethylpolysiloxane blocked with dimethylhydrogensiloxy group at both ends of molecular chain, dimethylsiloxane / methylhydrogensiloxane copolymer with blocked trimethylsiloxy group at both ends of molecular chain, and methylation of some of the methyl groups of these polysiloxanes Examples thereof include silicone oils such as polysiloxanes substituted with alkyl groups other than the groups, phenyl groups, and 3,3,3-trifluoropropyl groups.
[0016]
In addition, (A) the reaction for forming the cured silicone powder is a condensation reaction, and (A) the curable silicone composition for forming the cured silicone powder contains an uncrosslinked silicone oil in advance. In addition to the above non-reactive silicone oil, the non-cross-linked silicone oil includes a silicone oil such as polysiloxane in which a part of the methyl group of the non-reactive silicone oil is substituted with an alkenyl group, May be involved in this condensation reaction, but remained unreacted molecular chain both ends silanol-blocked dimethylpolysiloxane, a part of the methyl group of this polysiloxane is an alkyl group other than a methyl group, an alkenyl group, a phenyl group, Examples thereof include silicone oil substituted with 3,3,3-trifluoropropyl group.
In addition, when (A) the cured silicone powder is impregnated with a non-crosslinked silicone oil later, the type of the silicone oil is not particularly limited.
[0017]
Non-crosslinked organic oils include liquid paraffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, oleic acid Decyl, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol, cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cacao oil, jojoba oil, sesame oil, safflower oil, large Bean oil, camellia oil, squalane, persic oil, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, beef tallow, lard, polypropylene glycol monooleate, neopentyl glycol-2-ethylhexanoe Isostearic acid triglyceride, polyhydric alcohol ester oils such as coconut oil fatty acid triglyceride; glycol ester oils such as preparative polyoxyethylene lauryl ether, polyoxyalkylene ether oils such as polyoxypropylene cetyl ether and the like. These organic oils may be previously contained in the curable silicone composition for forming (A) cured silicone powder, or may be impregnated in (A) cured silicone powder.
[0018]
These non-crosslinked oils are liquid, and the viscosity at 25 ° C. is preferably in the range of 1 to 100,000 centipoise, for example, and more preferably in the range of 5 to 50,000 centipoise. In particular, it is preferably in the range of 5 to 10,000 centipoise. This is because an oil having a viscosity at 25 ° C. smaller than this range is volatile and tends to make it difficult to impart continuous water repellency to the resulting composite cured silicone powder, whereas an oil larger than this range This is because there is a tendency that it is difficult to form a cured silicone powder having an average particle diameter of 100 μm or less, and it is difficult to impregnate the cured silicone powder. Such a non-crosslinked oil is preferably the above-described silicone oil because it has excellent affinity with the cured silicone powder and can impart continuous water repellency to the composite cured silicone powder.
[0019]
(A) Content of the non-crosslinked oil contained in the cured silicone powder is, for example, 80% by mass or less in the (A) cured silicone powder containing the non-crosslinked oil, and ranges from 10 to 50% by mass. It is preferable to be within. This is because when (A) the content of the non-crosslinked oil in the cured silicone powder exceeds this range, the mechanical strength of the (A) cured silicone powder is reduced or the resulting composite cured silicone powder is uncrosslinked. This is because the oil tends to ooze out even under normal conditions. On the other hand, when the content of the non-crosslinked oil in the (A) cured silicone powder is less than 10% by mass, it tends to be difficult to impart sufficient hydrophilicity to the obtained composite cured silicone powder.
[0020]
(A) As a method for preparing a cured silicone powder, for example, a method of pulverizing a cured silicone product obtained by curing a curable silicone composition such as the following (i) to (iii) using a grinder such as a grinder A method in which a curable silicone composition such as the following (i) to (iii) is sprayed and cured by a sprayer such as a spray dryer; and a curable silicone composition such as the following (i) to (iii) is water or an interface A method of dispersing in an aqueous activator solution and curing is exemplified.
[0021]
(I) An organopolysiloxane having at least two alkenyl groups in one molecule, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, a non-crosslinkable oil, and a platinum-based compound Addition reaction curable silicone composition.
(Ii) an organopolysiloxane having a hydrolyzable group such as a hydroxyl group or an alkoxy group, an oxime group, an acetoxy group or an aminoxy group bonded to at least two silicon atoms in one molecule, or at least three silicon atoms in one molecule; Condensation comprising silane-based crosslinkers having hydrolyzable groups such as alkoxy groups, oxime groups, acetoxy groups, and aminoxy groups bonded to atoms, non-crosslinkable oils, and condensation reaction catalysts such as organotin compounds and organotitanium compounds Reaction curable silicone composition.
(Iii) An organic peroxide-curable silicone composition comprising a diorganopolysiloxane having at least one alkenyl group in one molecule, a non-crosslinkable oil, and an organic peroxide.
[0022]
Among these methods for preparing the (A) cured silicone powder, since the spherical (A) cured silicone powder having excellent dispersibility in the aqueous composition can be obtained, the curable silicone composition is used as water or a surfactant aqueous solution. The method of dispersing in and curing is particularly preferred.
[0023]
In order to prepare an aqueous dispersion of the curable silicone composition, for example, a stirring device such as a homogenizer or a colloid mill or a mixing device such as an ultrasonic vibrator can be used. At this time, before preparing the aqueous dispersion of the curable silicone composition, it is preferable to cool the curable silicone composition in advance to control its curability.
[0024]
In order to stabilize the curable silicone composition as particles in the aqueous dispersion, it is preferable to use an aqueous solution of a surfactant. The addition amount of the surfactant is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the curable silicone composition, and 0.5 to 5 parts by mass is particularly preferred. The surfactant added here is different from [(C) surfactant] described later, and is an optional component. Moreover, it is preferable that it is 40-2000 mass parts with respect to 100 mass parts of curable silicone compositions, and, as for the addition amount of water, it is especially preferable that it is 40-1000 mass parts. This is because when the amount of water added is less than 40 parts by mass with respect to 100 parts by mass of the curable silicone composition, it is difficult to form a uniform aqueous dispersion of the curable silicone composition. If the amount exceeds mass parts, the productivity of the (A) cured silicone powder is remarkably deteriorated.
[0025]
The water used is preferably stable in the aqueous dispersion of the curable silicone composition, so that it has a low metal ion and halogen ion, and preferably has an electric conductivity of 1 μS / cm or less. Is preferably ion-exchanged water of 0.5 μS / cm or less.
[0026]
Next, the aqueous dispersion of the curable silicone composition prepared by the above method is heated or allowed to stand at room temperature to cure the curable silicone composition in the aqueous dispersion, and (A) cured silicone. An aqueous dispersion of powder can be prepared.
When the aqueous dispersion of the curable silicone composition is heated, the heating temperature is preferably 100 ° C. or less, and particularly preferably 10 to 95 ° C. Examples of the method of heating the aqueous dispersion of the curable silicone composition include a method of directly heating the aqueous dispersion and a method of adding the aqueous dispersion to hot water.
[0027]
Subsequently, (A) cured silicone powder can be prepared by removing water from the aqueous dispersion of (A) cured silicone powder. (A) As a method of removing water from the aqueous dispersion of the cured silicone powder, for example, a method of drying using a vacuum dryer, a hot air circulation oven, or a spray dryer can be used.
[0028]
[(B) Inorganic fine powder]
(B) The inorganic fine powder is present in the composite cured silicone powder of the present invention in a state in which at least a part thereof is attached to the surface of the (A) cured silicone powder. The term “adhesion” as used herein means that (A) the surface of the cured silicone powder is covered with (B) an inorganic fine powder so as to cover the entire cured silicone powder, or (A) the cured silicone powder This refers to the state where (B) inorganic fine powder is unevenly distributed on a part of the surface. Moreover, a part of (B) inorganic fine powder may exist in the composite cured silicone powder of the present invention in a state of falling off from the surface of the (A) cured silicone powder.
[0029]
(B) At least a part of the inorganic fine powder is adhered to the surface of the (A) cured silicone powder, so that (A) aggregation of the cured silicone powder is suppressed, and the fluidity of the composite cured silicone powder of the present invention. , Improve dispersibility.
(B) Examples of the inorganic fine powder include metal oxide fine powders such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide and antimony oxide; metal nitride fine powders such as boron nitride and aluminum nitride; aluminum hydroxide, Metal hydroxide fine powder such as magnesium hydroxide; Metal carbonate such as calcium carbonate; Metal fine particles such as nickel, cobalt, iron, copper, gold, silver; Mica, talc, kaolinite, smectite, halloysite, pyrophyllite , Clay minerals such as vermiculite and montmorillonite; in addition, fine sulfide powder and fine chloride powder. Among these, metal oxide fine powder is preferable because it is advantageous in terms of cost due to availability, and silica fine powder is particularly preferable. Moreover, the surface of (B) inorganic fine powder may be previously hydrophobized with an organosilicon compound such as organoalkoxysilane, organochlorosilane, or organosilazane.
[0030]
The particle diameter of the (B) inorganic fine powder may be any particle diameter that can adhere to the surface of the (A) cured silicone powder, and specifically, 1/10 of the average particle diameter of the (A) cured silicone powder. The following particle diameter is preferable. Further, (B) the inorganic fine powder may be secondary agglomerated particles, but from the viewpoint of the effect of imparting dispersibility, this specific surface area is 10 m.2/ G or more is preferable. Here, the specific surface area is a value based on the BET specific surface area.
[0031]
[(C) Surfactant]
The (C) surfactant is present in the composite cured silicone powder of the present invention in a state where at least a part thereof is attached to the surface of the (B) inorganic fine powder. The term “adhesion” as used herein means that (B) the surface of the inorganic fine powder is covered or adsorbed on the surface of (B) the inorganic fine powder, or (B) the inorganic fine powder is covered. This refers to the state where (C) the surfactant is unevenly distributed on a part of the surface of the powder. Further, a part of the (C) surfactant may be present in the composite cured silicone powder of the present invention in a state of being attached and absorbed on the surface of the (A) cured silicone powder.
[0032]
(C) Surfactant is a component that improves the hydrophilicity of the composite cured silicone powder of the present invention by being present in the composite cured silicone powder of the present invention while adhering to the surface of the (B) inorganic fine powder. It is.
Examples of (C) surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and mixtures of two or more thereof. Among these, nonionic surfactants are preferable from the viewpoint of dispersibility of the obtained composite cured silicone particles. As the nonionic surfactant, a lipophilic or hydrophilic nonionic surfactant can be used.
[0033]
Examples of the lipophilic nonionic surfactant include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2- Sorbitan fatty acid esters such as diglycerol sorbitan ethylhexylate and diglycerol sorbitan tetra-2-ethylhexylate; mono-cotton oil fatty acid glycerin, monoerucic acid glycerin, glyceryl sesquioleate, glyceryl monostearate, α, α'-oleic acid pyroglutamic acid Glycerin fatty acids such as glycerin, glyceryl monostearate, and glyceryl malate; propylene glycol fatty acid esters such as propylene glycol monostearate Ethers, hardened castor oil derivatives, glycerin alkyl ether.
[0034]
Examples of hydrophilic nonionic surfactants include POE sorbitan fatty acid esters such as polyoxyethylene (hereinafter referred to as POE) sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate, and POE sorbitan tetraoleate; POE sorbit POE sorbite fatty acid esters such as monolaurate, POE sorbite monooleate, POE sorbite pentaoleate, POE sorbite monostearate; POE glycerol monostearate, POE glycerol monoisostearate, POE glycerol triisostearate, etc. POE glycerin fatty acid esters; POE monooleate, POE monostearate, POE distearate, POE monodiolate, ethylene glycol stearate POE fatty acid esters such as Cole; POE alkyl ethers such as POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether; POE octyl phenyl ether, POE nonyl POE alkyl phenyl ethers such as phenyl ether and POE dinonyl phenyl ether; Pluronic types such as pluronic (polyoxyethylene / polyoxypropylene glycol), POE / polyoxypropylene (hereinafter referred to as POP) cetyl ether, POE / POP- POE / PO such as 2-decyltetradecyl ether, POE / POP monobutyl ether, POE / POP hydrogenated lanolin, POE / POP glycerin ether, etc. Tetra POE / Tetra POP ethylenediamine condensates such as Tetronic; POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil mono Pyroglutamic acid monoisostearic acid diester, POE castor oil hardened castor oil derivatives such as POE hydrogenated castor oil maleic acid; POE beeswax lanolin derivatives such as POE sorbit beeswax; coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc. Alkanolamide, POE propylene glycol fatty acid ester, POE alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde condensate, Alkyl ethoxy dimethyl amine oxide, trioleyl phosphoric acid, etc. are mentioned.
[0035]
Examples of silicone surfactants include dimethylpolysiloxane-polyethylene glycols, dimethylpolysiloxane polyethylenes, dimethylpolysiloxane polyethylene glycol copolymers, dimethylpolysiloxane / methyl (polyoxyethylene) siloxane copolymers, and the like. It is done.
Among these nonionic surfactants, polyethylene oxide group-containing nonionic surfactants are preferred because they are easy to handle as liquids when blended. Particularly, as the alkyl ether of polyethylene oxide, at least 10 of the alkyl groups in the alkyl ether are preferred. Those whose mass% is an alkyl group having 13 carbon atoms or polyoxyethylene sorbate monolauryl ether are preferred. One or more of these nonionic active agents can be arbitrarily selected and used.
[0036]
[Composite cured silicone powder]
The amount of (B) inorganic fine particles and (C) surfactant attached to the (A) cured silicone powder is not particularly limited as long as the adjusted composite cured silicone particles have sufficient fluidity and hydrophilicity. . In addition, depending on the particle size of the (A) cured silicone powder, the adhesion amount of (B) inorganic fine particles and (C) surfactant varies, but the adhesion amount of (B) inorganic fine particles and (C) surfactant is Preferably, (A) 0.1 to 30 parts by mass of inorganic fine particles and (C) a surfactant is 0.1 to 30 parts by mass with respect to 100 parts by mass of (A) cured silicone powder. Particularly preferably, (A) 0.2 to 10 parts by mass of the inorganic fine particles and (C) 0.2 to 10 parts by mass of the surfactant per 100 parts by mass of the cured silicone powder. This is because when the amount of (B) inorganic fine particles or (C) surfactant is outside this range, the fluidity tends to deteriorate or the hydrophilicity tends to be difficult to improve.
[0037]
Next, the method for producing the composite cured silicone powder of the present invention will be described in detail.
The composite cured silicone powder of the present invention is(A) A cured silicone powder having an average particle size of 0.1 to 500 μm and (B) an inorganic fine powder are mixed under mechanical shearing, and then this and (C) a surfactant are mixed under mechanical shearing. MixIt is manufactured by.
Examples of the apparatus for mixing these components (A) to (C) under mechanical shear include a Henschel mixer and a super mixer.
Moreover, the temperature at the time of mixing these (A)-(C) components is not specifically limited, For example, it can also carry out under room temperature. Also, the mixing time is such that (A) cured silicone powder having poor fluidity exhibits fluidity due to (B) inorganic fine powder adhering to this surface, so by observing the change in this state, It is necessary to decide accordingly.
[0038]
In the method for producing a composite cured silicone powder of the present invention, (A) cured silicone powder and (B) inorganic fine powder are mixed in advance, and then (C) a surfactant is added thereto and mixed.TheThis is because (A) the surfactant is localized in (B) inorganic fine particles attached to the surface of (A) the cured silicone powder, thereby improving the hydrophilicity of the composite cured silicone powder.
[0039]
In the method for producing a composite cured silicone powder of the present invention, the amount of (B) inorganic fine powder added may be an amount sufficient to coat the surface of (A) cured silicone powder, and (A) cured silicone. Although it varies depending on the content of non-crosslinked oil contained in the powder, it is usually preferably 0.1 to 100 parts by mass, particularly 1 to 50 parts per 100 parts by mass of the (A) cured silicone powder. It is preferable that it is a mass part.
[0040]
In the method for producing a composite cured silicone powder of the present invention, the amount of (C) surfactant added may be an amount that imparts sufficient hydrophilicity to the composite cured silicone powder. Although it varies depending on the blending amount of the (B) inorganic fine powder to be added, it is usually preferably 0.1 to 100 parts by mass, particularly 0.5 to 100 parts by mass with respect to 100 parts by mass of the (A) cured silicone powder. It is preferably 50 parts by mass.
[0041]
[Aqueous composition]
The aqueous composition of the present invention is an aqueous composition containing the composite cured silicone powder of the present invention.
Examples of the aqueous composition containing the composite cured silicone powder of the present invention include curable resin compositions dispersed in an aqueous medium, non-curable resin compositions, and liquid compositions such as cosmetics in aqueous dispersion. The amount of water in the aqueous composition is not particularly limited, and may be an amount in which an aqueous medium is present as the matrix phase since the composite cured silicone powder of the present invention is easily dispersed in the aqueous phase.
[0042]
In the composite cured silicone powder of the present invention described above, (B) inorganic fine powder adheres to (A) cured silicone powder having an average particle size of 0.1 to 500 μm, and (B) inorganic fine powder (C). Since the surfactant is attached, the hydrophilicity is improved by the surfactant (C) without impairing the improvement of fluidity and dispersibility by the inorganic fine powder (B). That is, when (B) inorganic fine powder is not present on the surface of (A) cured silicone powder and (C) surfactant alone is attached to the surface of (A) cured silicone powder, (C) surfactant (A) promotes agglomeration of the cured silicone powder and deteriorates the dispersibility. However, (B) by attaching the inorganic fine powder to the surface of the (A) cured silicone powder, (C) the surfactant is (B It is unevenly distributed in the inorganic fine powder, and (C) aggregation of the cured silicone powder by the surfactant is suppressed, and at the same time, hydrophilicity by the surfactant (C) is imparted to the composite cured silicone powder.
[0043]
Since the composite cured silicone powder of the present invention has excellent fluidity, hydrophilicity, and dispersibility, it has excellent affinity and dispersibility for aqueous compositions. Therefore, the composite cured silicone powder of the present invention can be used as an additive or a modifier for matting, feel improvement, crack prevention, low elasticity, etc. of aqueous compositions such as aqueous paints and aqueous cosmetics. it can.
[0044]
[Example]
The composite cured silicone powder of the present invention and the production method thereof will be described in detail with reference to examples.
The viscosity in this example is a value measured at 25 ° C.
(A) The characteristics of the cured silicone powder and the composite cured silicone powder were measured as follows.
[JIS A hardness of cured silicone powder]
(A) The curable silicone composition which is a raw material of the cured silicone powder was cured into a sheet shape, and the hardness was measured with a JIS A hardness meter defined in JIS K 6301.
[0045]
[Content of non-crosslinked oil in cured silicone powder]
(A) A dispersion is prepared by adding 1000 g of toluene to 100 g of the cured silicone powder. The dispersion is stirred at 1000 rpm for 10 minutes using a stirrer, for example, a homodisper, and further at 500 rpm for 10 minutes. Allowed to stand for 12 hours. Thereafter, this dispersion was again stirred with a homodisper at 500 rpm for 10 minutes. The dispersion was filtered through filter paper, and the filtrate was collected. Then, 750 g of toluene was added to the cured silicone powder remaining on the filter paper to prepare a dispersion, and this dispersion was stirred at 1000 rpm for 10 minutes using a homodisper. The dispersion was filtered through filter paper, and the filtrate was collected. This filtrate was combined with the previously collected filtrate, and toluene was distilled off at 80 ° C. under a condition of 70 mmHg using an evaporator. The viscosity and mass of the obtained oil were measured. In addition, this oil was subjected to proton nuclear magnetic resonance spectrum analysis, gel permeation chromatographic analysis, and infrared spectroscopic analysis to identify the components of this oil.
[0046]
[Average particle size]
(A) An aqueous dispersion or ethanol dispersion of cured silicone powder or composite cured silicone powder was measured with a laser diffraction particle size distribution analyzer (LA-500 from Horiba, Ltd.), and the median diameter (corresponding to 50% of cumulative distribution) The average particle size was determined as the average particle size.
[Liquidity]
(A) Measuring mass% of these powders in which cured silicone powder or composite cured silicone powder is meshed on at 100 mesh (aperture = 150 μm) using an Alpine air jet sieve sieve machine. It was evaluated by.
[0047]
[Hydrophilic]
1 g of (A) cured silicone powder or composite cured silicone powder was added to 100 ml of water and mixed with a stirrer. (A) A cured silicone powder or composite cured silicone powder that does not conform to water and is left floating on the water surface is indicated as water repellency (XX), and that that conforms to water but does not disperse in water (×) Those that disperse in water were marked with (◯).
[0048]
Each component used in this example is as follows.
[(A) Cured silicone powder]
(A-1) Addition-curable polydimethylsiloxane silicone rubber powder: 0.2% by mass of a nonionic surfactant, 2.8% by mass of a 20-30 mer polydimethylsiloxane cyclic product, average particle diameter 4 μm, JIS-A hardness: 30.
(A-2) Addition-curable polydimethylsiloxane silicone rubber powder: containing 1.5% by mass of a nonionic surfactant, containing 2.8% by mass of a 20-30 mer polydimethylsiloxane cyclic product, and average particle diameter 4 μm, JIS-A hardness: 30.
[0049]
[(B) Inorganic fine particles]
Aerosil 200: manufactured by Nippon Aerosil Co., Ltd., average primary particle size of 5 to 15 nm, BET specific surface area of 200 m2/ G, dry method silica, surface silanol density 4.2 pieces / nm2.
[(C) Surfactant]
Mixture of secondary dodecyl ether and secondary tridecyl ether of ethylene oxide (12 mol addition): 43% by mass of dodecyl group, 57% by mass of tridecyl group, HLB = 14.5
[0050]
[Example 1]
(A-1) Silicone rubber powder is put into a super mixer (Henschel type mixer, Kawata V-20, internal volume 20 L) and stirred at room temperature for about 2 minutes at a rotational speed of 2,000 rpm to form a block-like lump. Crushed. To this, (B) inorganic fine particles were added and mixed for 3 minutes at a rotation speed of 2000 at room temperature. Further, (C) a surfactant was added and mixed for 2 minutes at a rotation speed of 2000 rotations at room temperature. Here, the mass ratio (A-1 / B / C) = 20/2 so that the total amount of (A-1) silicone rubber powder, (B) inorganic fine particles, and (C) surfactant is 1 kg. .9 / 1.1.
The resulting composite cured silicone powder was evaluated for hydrophilicity and fluidity and listed in Table 1.
[0051]
[Example 2, Comparative Examples 1 to 4]
(A) Composite cured silicone powder as in Example 1 except that the type and blending amount of the cured silicone powder, (B) inorganic fine particles, and (C) the blending amount of the surfactant were changed as shown in Table 1. Alternatively, a cured silicone powder was obtained.
The obtained composite cured silicone powder and cured silicone powder were evaluated for hydrophilicity and fluidity, and are listed in Table 1.
[0052]
[Table 1]
[Example 3]
40 parts by mass of composite cured silicone particles of Example 1, 1 part by mass of silicone-treated titanium oxide, 5 parts by mass of octyl p-methoxycinnamate, 10 parts by mass of trimethylsiloxy group-capped dimethylpolysiloxane having a molecular chain both ends with a viscosity of 20 mPa · s, Polyoxyethylene (40 mol adduct) hardened castor oil 3 parts by weight, squalane 30 parts by weight, glycerin 5 parts by weight, beeswax 3 parts by weight, preservative appropriate amount, perfume appropriate amount and purified water appropriate amount 1, the creamy cosmetic product of Example 3 was prepared by stirring for 5 minutes with an internal volume of 58.5 cc). The evaluation results of this cosmetic are shown in Table 2.
Here, the particle size of the composite cured silicone particles in the cosmetic was calculated by the number of the particles in the cosmetic spread on the glass plate observed with an optical microscope. Formulation was judged by the degree of increase in the viscosity of creamy cosmetics. In other words, poor dispersion is a significant increase in viscosity.
[0054]
[Example 4, Comparative Examples 5 to 7]
Example 4 and Comparative Examples 5 to 7 were the same as Example 3 except that the composite cured silicone particles were changed to the composite cured silicone particles of Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 4. A cosmetic product was prepared. The evaluation results of this cosmetic are shown in Table 2.
[0055]
[Table 2]
[Example 5]
20 parts by mass of the composite cured silicone particles of Example 1 and 100 parts by mass of a water-based paint (water-colored glossy coat made by Campe Papio Co., Ltd., sky blue, acrylic resin-based paint) were mixed and stirred for 20 seconds with a dental mixer. An aqueous coating composition was prepared. The aqueous coating composition was applied to an aluminum plate while controlling the thickness of the coating film with a cellophane tape (40 μm thickness) affixed to the aluminum plate, and then left standing in a draft at room temperature for 1 week to dry. The thickness of the dried coating film was about 20-50 μm. The evaluation results of this aqueous coating composition are shown in Table 3 in the same manner as in Example 3.
Here, the dispersion state of the cured silicone particles in the coating film was calculated by the number of particles in the coating film observed with an optical microscope. The compounding property was judged by the degree of increase in the viscosity of the coating composition. In other words, poor dispersion is a significant increase in viscosity.
[0057]
[Example 6, Comparative Examples 8 and 9]
The aqueous paint compositions of Examples 6, 8 and 9 were the same as Example 5 except that the composite cured silicone particles were changed to the composite cured silicone particles of Example 2, Comparative Example 2 or Comparative Example 3. A product was prepared. The evaluation results of this water-based coating composition are shown in Table 3.
[0058]
[Table 3]
As explained above, the present inventionObtained by the manufacturing method ofIn the composite cured silicone powder, (B) inorganic fine powder adheres to (A) cured silicone powder having an average particle size of 0.1 to 500 μm, and (C) surfactant adheres to (B) inorganic fine powder. Therefore, it has excellent fluidity, hydrophilicity and dispersibility. An aqueous paint to which such a composite cured silicone powder is added has a uniform matte effect, and an aqueous cosmetic to which such a composite cured silicone powder is added has the advantage of good touch.
[0060]
The composite cured silicone powder of the present inventionManufacturing methodIs(A) A cured silicone powder having an average particle size of 0.1 to 500 μm and (B) an inorganic fine powder are mixed under mechanical shearing, and then this and (C) a surfactant are mixed under mechanical shearing. MixTherefore, it has excellent fluidity, hydrophilicity and dispersibility.
Moreover, if the (B) inorganic fine powder is a metal oxide fine powder, particularly silica, it is advantageous in terms of cost because of its availability.
The specific surface area of (B) inorganic fine powder is 10 m2If it is / g or more, it is preferable because it can impart more excellent fluidity.
In addition, if the (A) cured silicone powder is a silicone rubber powder, it is preferable because various properties can be imparted to the application.
[0061]
Also,In the method for producing a composite cured silicone powder of the present invention, (A) cured silicone powder and (B) inorganic fine powder are mixed under mechanical shearing, and then (C) surfactant is mechanically sheared. By mixing in step (b), a composite cured silicone powder having further improved fluidity, hydrophilicity and dispersibility can be obtained.
In addition, the aqueous composition of the present invention is the present invention.Obtained by the manufacturing method ofSince it contains a composite cured silicone powder, it is possible to obtain a water-based paint having a uniform matte effect and a water-based cosmetic having a good feel.
Claims (9)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002362557 | 2002-12-13 | ||
| JP2002362557 | 2002-12-13 | ||
| PCT/JP2003/015690 WO2004055099A1 (en) | 2002-12-13 | 2003-12-08 | Composite cured silicone powder, method for production thereof and aqueous composition |
Publications (2)
| Publication Number | Publication Date |
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| JPWO2004055099A1 JPWO2004055099A1 (en) | 2006-04-20 |
| JP4646632B2 true JP4646632B2 (en) | 2011-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2004560610A Expired - Fee Related JP4646632B2 (en) | 2002-12-13 | 2003-12-08 | Method for producing composite cured silicone powder and aqueous composition |
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| Country | Link |
|---|---|
| US (1) | US7399803B2 (en) |
| EP (1) | EP1584642B1 (en) |
| JP (1) | JP4646632B2 (en) |
| KR (1) | KR100994353B1 (en) |
| AU (1) | AU2003289247A1 (en) |
| WO (1) | WO2004055099A1 (en) |
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| JP4931350B2 (en) * | 2005-01-05 | 2012-05-16 | 東レ・ダウコーニング株式会社 | Composite silicone rubber powder, method for producing the same, paint, and cosmetic |
| DE102006014875A1 (en) * | 2006-03-30 | 2007-10-04 | Wacker Chemie Ag | Particle, useful in e.g. a surface coating and a molded body, comprises a polymerization product of a polyadditionable, polycondensable or polymerizable siloxane and/or silane; and solid particulates |
| JP5024205B2 (en) * | 2007-07-12 | 2012-09-12 | 三菱瓦斯化学株式会社 | Prepreg and laminate |
| JP5864828B2 (en) * | 2007-08-31 | 2016-02-17 | 東レ・ダウコーニング株式会社 | Silicone rubber powder and method for producing the same |
| JP2009057500A (en) * | 2007-08-31 | 2009-03-19 | Dow Corning Toray Co Ltd | Curable epoxy resin composition and its cured material |
| JP5698444B2 (en) * | 2009-07-27 | 2015-04-08 | 東レ・ダウコーニング株式会社 | Composite cured silicone powder and method for producing the same |
| JP5229187B2 (en) * | 2009-11-11 | 2013-07-03 | 信越化学工業株式会社 | Silicone composite particles, production method thereof, and cosmetics |
| US20130149261A1 (en) | 2010-08-23 | 2013-06-13 | Dow Corning Corporation | Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use |
| CN103154093B (en) | 2010-08-23 | 2015-08-26 | 道康宁公司 | Sugar silicone copolymers and preparation and application thereof |
| US9492369B2 (en) | 2010-08-23 | 2016-11-15 | Dow Corning Corporation | Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use |
| JP5607001B2 (en) | 2011-08-11 | 2014-10-15 | 信越化学工業株式会社 | Silicone fine particles and method for producing the same |
| CN104136503A (en) * | 2012-02-07 | 2014-11-05 | 道康宁(中国)投资有限公司 | Aqueous suspension of composite silicone powder, w/o emulsion and cosmetics |
| JP5996085B2 (en) | 2013-02-27 | 2016-09-21 | 株式会社朝日ラバー | White reflective film ink, white reflective film powder coating, and white reflective film manufacturing method |
| JP6304803B2 (en) * | 2014-01-20 | 2018-04-04 | 日本化薬株式会社 | Method for producing resin composition |
| JP6707516B2 (en) * | 2015-02-25 | 2020-06-10 | ダウ・東レ株式会社 | Curable granular silicone composition and method for producing the same |
| JP6859015B2 (en) | 2015-10-28 | 2021-04-14 | ダウ・東レ株式会社 | Cosmetic composition and cosmetics and external preparations for skin |
| EP3572475A4 (en) * | 2017-01-19 | 2020-02-05 | Panasonic Intellectual Property Management Co., Ltd. | Coating composition, optical member, and illuminator |
| EP4047038A4 (en) * | 2019-10-15 | 2023-10-18 | Sekisui Chemical Co., Ltd. | Optical bonding particles, adhesive, and display device |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20060058440A1 (en) | 2006-03-16 |
| EP1584642A1 (en) | 2005-10-12 |
| EP1584642B1 (en) | 2012-08-08 |
| AU2003289247A1 (en) | 2004-07-09 |
| US7399803B2 (en) | 2008-07-15 |
| KR20050092700A (en) | 2005-09-22 |
| JPWO2004055099A1 (en) | 2006-04-20 |
| KR100994353B1 (en) | 2010-11-16 |
| EP1584642A4 (en) | 2008-06-11 |
| WO2004055099A1 (en) | 2004-07-01 |
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